The preparation of optically active, especially enantiomerically pure, organic molecules is a challenging topic in chemistry. This issue has attracted widespread attention and has been studied for decades. Among these molecules there are a large number of sulfur-containing derivatives whose chirality results from the presence of a stereogenic sulfur atom with different valence and coordination numbers. Recently, they have gained great interest as biologically active compounds, components of new materials, as well as reagents, catalysts, and/or auxiliary agents that can be used effectively in asymmetric synthesis. This chapter is devoted to the presentation of the main groups of optically active sulfur derivatives and the most common approaches that have made it possible to isolate them as optically active forms and their selected synthetic applications.